TWI682476B - Device and method for bonding substrates - Google Patents
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- TWI682476B TWI682476B TW103124297A TW103124297A TWI682476B TW I682476 B TWI682476 B TW I682476B TW 103124297 A TW103124297 A TW 103124297A TW 103124297 A TW103124297 A TW 103124297A TW I682476 B TWI682476 B TW I682476B
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
- H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
- H01L21/2007—Bonding of semiconductor wafers to insulating substrates or to semiconducting substrates using an intermediate insulating layer
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/185—Joining of semiconductor bodies for junction formation
- H01L21/187—Joining of semiconductor bodies for junction formation by direct bonding
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
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Abstract
Description
本發明係關於根據技術方案1之一種用於在一第一基板之一結合側與一第二基板之一結合側之間產生一導電直接結合之裝置，及根據技術方案7之一種對應方法。
The present invention relates to a device for generating a conductive direct bond between a bonding side of a first substrate and a bonding side of a second substrate according to
尤其在結合金屬或金屬化基板、具有金屬表面之基板、半導體基板，或化合物半導體基板時，由於待結合之基板之結合側之氧化阻礙結合處理，故其發揮一顯著作用。氧化物阻止或減少一機械及/或電寶貴接觸件之形成。歸因於較長加熱及冷卻時間，顯著與此相關聯的係產量之一下降；且結合期間溫度愈高或必須愈高，則歸因於溫差之膨脹對基板相對於彼此之對準或調整精確度之影響愈大。此外，某些MEMS及/或半導體總成(例如，諸如微晶片或記憶體晶片)不容許高處理溫度。 Especially when bonding a metal or metallized substrate, a substrate with a metal surface, a semiconductor substrate, or a compound semiconductor substrate, since the oxidation of the bonding side of the substrate to be bonded hinders the bonding process, it plays a significant role. Oxides prevent or reduce the formation of a mechanical and/or electrical valuable contact. Due to the longer heating and cooling time, one of the production volumes associated with this is significantly reduced; and the higher or must be the higher the temperature during the bonding, due to the alignment or adjustment of the substrate relative to each other due to the expansion of the temperature difference The greater the impact of accuracy. In addition, certain MEMS and/or semiconductor assemblies (eg, such as microchips or memory chips) do not allow high processing temperatures.
在當前最先進技術中，主要濕式蝕刻處理用於移除形成於上文提及之基板上且因此阻止或至少阻礙多個基板藉由一結合處理之一最佳結合之氧化物。在濕式蝕刻處理中，主要使用氫氟酸或含氫氟酸之混合物。在還原氧化物之後，出現藉由氫原子終止之一表面。此等疏水表面適用於產生一所謂預結合。然而，若兩個晶圓變成永久彼此連接，則必須在高溫下加熱加工晶圓堆疊，使得自結合介面移除藉由還原處理產生且終止基板之表面之氫，且可在兩個基板表面(尤其矽表面)之間形成一永久連接。在表面進行接觸之後加熱加工基板堆疊。 在接近700℃之一溫度下(例如)加熱加工矽晶圓以確保此一永久連接。此項技術中之方法尤其用以產生多層金屬、半導體、玻璃，或陶瓷結合。一尤其重要應用係關於光伏打多層電池及光子晶體，尤其由矽製成之光子晶體之產生。 In the current state-of-the-art technology, the main wet etching process is used to remove oxides formed on the above-mentioned substrates and thus prevent or at least hinder the optimal bonding of a plurality of substrates by a bonding process. In the wet etching process, hydrofluoric acid or a mixture containing hydrofluoric acid is mainly used. After reducing the oxide, a surface terminated by hydrogen atoms appears. These hydrophobic surfaces are suitable for creating a so-called pre-bond. However, if the two wafers become permanently connected to each other, the wafer stack must be heated and processed at a high temperature, so that the self-bonding interface removes the hydrogen generated by the reduction process and terminates the surface of the substrate, and can be on both substrate surfaces ( Especially the silicon surface forms a permanent connection. After contacting the surfaces, the substrate stack is heat-processed. The silicon wafer is heat-processed at a temperature close to 700°C, for example, to ensure this permanent connection. The method in this technique is especially used to produce multilayer metal, semiconductor, glass, or ceramic combinations. One particularly important application relates to the production of photovoltaic multi-layer cells and photonic crystals, especially photonic crystals made of silicon.
產生多層電池之主要限制之一者係個別半導體材料之晶格結構相對於其等大小及形狀之不相容性。在藉由層之直接磊晶生長之個別層之產生中，此導致藉由此處理產生之半導體層中之缺陷。此等缺陷包括經產生層之品質及尤其可在將光轉換成電能中實現之效率。此效率亦係指量子效率且針對太陽能電池定義可由光子處理使用之電荷載體對一特定波長之經吸收光子之量之比率。在實踐中，自此出現關於下列參數之約束： One of the main limitations for producing multilayer batteries is the incompatibility of the lattice structure of individual semiconductor materials with respect to their equal size and shape. In the production of individual layers grown by direct epitaxial growth of the layers, this leads to defects in the semiconductor layer produced by this process. Such defects include the quality of the resulting layer and the efficiency that can be achieved especially in the conversion of light into electrical energy. This efficiency also refers to quantum efficiency and defines for solar cells the ratio of charge carriers that can be used by photon processing to the amount of absorbed photons of a specific wavelength. In practice, there have been constraints on the following parameters since then:
a)結構中之可行主動層之數目。即，歸因於上文描述之困難，限制於兩層或最大三層。 a) The number of feasible active layers in the structure. That is, due to the difficulty described above, it is limited to two layers or a maximum of three layers.
b)關於一最佳波長範圍之個別層之最佳化。在實踐中，由於始終必須關於晶格結構之相容性進行折衷，故今天不可能關於最佳波長範圍及自光轉換成電能之相關聯轉換特性完全自由地最佳化個別層。 b) Optimization of individual layers in an optimal wavelength range. In practice, since compromises must always be made regarding the compatibility of the lattice structure, it is not possible today to completely freely optimize individual layers with regard to the optimal wavelength range and the associated conversion characteristics of conversion from light to electrical energy.
c)使用較佳材料：針對某些波長期望使用矽或鍺(例如)，其係因為此等材料將容許效率與成本之間之一理想折衷。然而，使用此等材料常常係不可能的，其係因為晶格結構與用於電池中之其他結構不夠相容。 c) Use of better materials: It is desirable to use silicon or germanium (for example) for certain wavelengths because these materials will allow an ideal compromise between efficiency and cost. However, it is often impossible to use these materials because the lattice structure is not sufficiently compatible with other structures used in batteries.
在一後續結合處理之前，常常使用氫氟酸執行氧化物加工，尤其氧化物移除。在處理中，在氧化物移除之後可發生表面之污染且尤其氧化物之再生長。 Prior to a subsequent bonding process, hydrofluoric acid is often used to perform oxide processing, especially oxide removal. During the treatment, contamination of the surface and especially regrowth of oxides can occur after the oxides are removed.
此方面之一進一步問題係氧化物移除與基板之進一步加工之間之一可變等待時期導致經結合基板堆疊之一可變處理結果。 A further problem in this regard is that a variable waiting period between oxide removal and further processing of the substrate results in a variable processing result of the bonded substrate stack.
先前方法之一進一步缺點係必須對待蝕刻之氧化物裁適蝕刻處 理。因此，某些情況下對於不同半導體材料需要不同蝕刻化學品。 One further disadvantage of the previous method is that the etched oxide must be tailored to the etched area Management. Therefore, in some cases, different etching chemicals are required for different semiconductor materials.
此外，某些情況下關於加工之前之等待時間、處理環境條件之種類(例如，惰性氣氛、無O2，且視需要亦無水分)之處理要求取決於材料亦不同。為此原因，用於結合由不同材料構成之不同基板之一結合系統結果可為相當複雜。此外，歸因於由各種材料施加之不同要求，新材料一經引入至製造中，即可引起大量處理發展努力。 In addition, in some cases, the processing requirements regarding the waiting time before processing and the type of processing environmental conditions (for example, inert atmosphere, no O2, and no moisture if necessary) depend on the material. For this reason, the result of one bonding system for bonding different substrates composed of different materials can be quite complicated. In addition, due to the different requirements imposed by various materials, the introduction of new materials into manufacturing can cause significant processing development efforts.
除已提及之化學處理之外之物理處理表示用於氧化物移除之另一方法。用於氧化物移除之最重要物理處理之一者係濺射。濺射被定義為一基板之表面上之原子藉由經電離且由電及/或磁場加速之濺射氣體之經電離原子之碰撞處理之移除。 Physical treatment other than the chemical treatment already mentioned represents another method for oxide removal. One of the most important physical treatments for oxide removal is sputtering. Sputtering is defined as the removal of atoms on the surface of a substrate by ionized atom collision treatment of sputtering gas that is ionized and accelerated by electricity and/or magnetic field.
然而，由於處理固定地產生粒子，故濺射係不利的；此在於藉由一物理處理自一表面移除材料之處理之本質。此材料可被沈積在處理腔室之各個位置中且可藉由升華自此等位置沉澱至待結合之基板上或可直接再升華回至基板上。此等粒子係最佳(即，無空隙)結合結果之障礙。此外，濺射處理需要非常高的離子能量以能夠自基板之表面移除物質。此導致離子部分被植入基板中，其損害表面附近層。此經損害層可係數nm厚，通常甚至5nm至10nm或更大。此損害可負向影響關於電及光學參數之結合連接之特性，其中結果係此損害並非所要且在實踐中存在一問題。 However, since the process generates particles fixedly, sputtering is disadvantageous; this lies in the nature of the process of removing material from a surface by a physical process. This material can be deposited in various locations in the processing chamber and can be deposited from these locations by sublimation onto the substrate to be bonded or can be directly sublimated back onto the substrate. These particles are obstacles to the best (ie, no void) binding results. In addition, the sputtering process requires very high ion energy to be able to remove substances from the surface of the substrate. This causes ions to be partially implanted into the substrate, which damages the layer near the surface. This damaged layer may have a thickness of nm, usually even 5 nm to 10 nm or more. This damage can negatively affect the characteristics of the combined connection of electrical and optical parameters, with the result that this damage is undesirable and there is a problem in practice.
製造多層電池中之另一基本問題係通常用於許多處理之熱加工。在100℃與700℃之間進行熱加工。在此等高溫下，機械地強烈加應力於使用之材料。在高溫差之存在下，尤其藉由熱應力判定機械應變。熱應力取決於熱膨脹係數及溫差。若材料因其等經沿著一結合介面焊接在一起而不可一起自由地膨脹，則在一溫差之存在下之熱膨脹係數之一差異導致對應高熱應力。由於相當常常藉由其他邊界條件判定材料之選擇，故僅可在處理步驟內之溫差盡可能小時避免熱 應力。 Another basic problem in the manufacture of multilayer batteries is the thermal processing commonly used in many processes. Hot processing is performed between 100°C and 700°C. At these high temperatures, the materials used are mechanically strongly stressed. In the presence of high temperature differences, mechanical strain is judged especially by thermal stress. Thermal stress depends on thermal expansion coefficient and temperature difference. If the materials cannot be freely expanded together by welding along a bonding interface due to their warp, a difference in the coefficient of thermal expansion in the presence of a temperature difference results in correspondingly high thermal stress. Since the choice of materials is often judged by other boundary conditions, the temperature difference in the processing step can only be as small as possible to avoid heat stress.
應提及藉由其結合處理應提供最大優點之材料組合(如具有不同晶格參數及/或不同熱膨脹係數之材料之整合應跟隨)與一熱加工處理最不相容，其係因為此處通常發生關於熱膨脹之最大差異。 It should be mentioned that the combination of materials that should provide the greatest advantage through its combined treatment (eg, the integration of materials with different lattice parameters and/or different coefficients of thermal expansion should be followed) is most incompatible with a hot working process, because here Usually the biggest difference in thermal expansion occurs.
因此，本發明之目的係指定藉由其可更有效且品質上更寶貴地執行結合處理之用於結合之一裝置及一方法。 Therefore, the object of the present invention is to specify a device and a method for bonding by which the bonding process can be performed more efficiently and more preciously in quality.
以技術方案1及7之特徵達成此任務。附屬技術方案中給出本發明之有利增強。本發明之範疇包含描述、申請專利範圍及/或圖式中給定之至少兩個特徵之所有組合。藉由給定值範圍，位於經提及之邊界內之值亦應被揭露為限制且應係可以任何組合要求。
This task is achieved with the features of
本發明描述用於一基板之氧化物層之電漿加工之一系統及一方法。藉此，根據本發明，電漿加工可導致氧化物層之一完全移除、一部分移除，及/或理想配比之一改變及/或完全層或至少表面附近層之一非晶化。 The present invention describes a system and a method for plasma processing of an oxide layer of a substrate. Thereby, according to the present invention, plasma processing may result in complete removal of one of the oxide layers, partial removal, and/or change in one of the ideal ratios and/or amorphization of the complete layer or at least one of the layers near the surface.
特定言之，本發明藉此實現氧化物層在一電漿腔室中之就地加工，其中電漿由至少一還原氣體(尤其氫)組成。 In particular, the present invention thereby achieves in-situ processing of the oxide layer in a plasma chamber, where the plasma is composed of at least one reducing gas, especially hydrogen.
藉由根據本發明之裝置及根據本發明之方法，可能完全在抵抗氣氛而密封之一工作空間(或在連接至工作空間之模組中)執行氧化物之加工及後續結合處理使得防止氧化物經加工之後表面之重新氧化。 With the device according to the present invention and the method according to the present invention, it is possible to completely seal a working space (or in a module connected to the working space) that is resistant to the atmosphere to perform oxide processing and subsequent bonding treatment so as to prevent oxides After processing, the surface is oxidized again.
本發明描述可能進行下列各項之一系統及一方法：(1)在一電漿腔室中藉由還原氣體製造具有一尤其經變更之氧化物層之多個基板，(2)在一真空環境中(尤其在一高度真空環境中)將基板傳輸至一結合模組，及(3)在結合模組中將基板彼此結合。 The present invention describes a system and a method that may perform one of the following: (1) manufacturing a plurality of substrates with an especially modified oxide layer from a reducing gas in a plasma chamber, (2) in a vacuum The substrate is transferred to a bonding module in an environment (especially in a high vacuum environment), and (3) the substrates are bonded to each other in the bonding module.
改質根據本發明被定義如下： ．沉澱期間及/或沉澱之後氧化物之理想配比之理想配比之變更，及/或．一特定量之一已存在氧化物層之移除，其達到一所要、新的氧化物層厚度，或．氧化物層之完全移除，及/或．氧化物層之非晶化。 Modification according to the invention is defined as follows: . Changes in the ideal ratio of oxides during and/or after precipitation, and/or. A certain amount of the removal of an existing oxide layer, which reaches a desired, new oxide layer thickness, or. Complete removal of the oxide layer, and/or. Amorphization of the oxide layer.
此係藉由可使基板暴露至含有一還原氣體之一電漿之一裝置完成。特定言之，發現H2用於具有至少一第二氣體(尤其一惰性氣體)之一混合物中。已證明H2/Ar混合物之使用係較佳變體。 This is accomplished by a device that exposes the substrate to a plasma containing a reducing gas. In particular, H 2 was found to be used in a mixture with at least a second gas, especially an inert gas. The use of the H 2 /Ar mixture has proven to be a preferred variant.
歸因於氬與氧之間之質量比，H2/Ar之氣體混合物係最佳的。某種程度上重於氧之氬原子被藉由電漿電離、被加速至待還原之氧化物上，且藉由動能使其物理地(尤其機械地)破裂。藉由氫分子、氫離子或氫基相應地捕獲藉由此處理釋放之氧。接著自表面汲取熱力學相對穩定之由此產生之水分以防止反向反應至金屬氧化物。氦歸因於其相當小的質量而不適合。氖原子誠然比氧原子更大，但僅邊緣如此。氪及所有其他稀有氣體太昂貴且太稀少且因此經濟上不值得用於破裂氧化物。 Due to the mass ratio between argon and oxygen, the H 2 /Ar gas mixture is the best. Argon atoms, which are somewhat heavier than oxygen, are ionized by plasma, accelerated to the oxide to be reduced, and physically (especially mechanically) broken by kinetic energy. The oxygen released by this treatment is captured accordingly by hydrogen molecules, hydrogen ions or hydrogen groups. Then the thermodynamically relatively stable resulting water is drawn from the surface to prevent reverse reaction to the metal oxide. Helium is not suitable due to its rather small mass. Neon atoms are indeed larger than oxygen atoms, but only at the edges. Krypton and all other rare gases are too expensive and too scarce and therefore not economically worthy of being used to crack oxides.
顯著地，根據本發明之其他還原氣體係：．一氧化氮．一氧化碳及/或．甲烷及/或．氫及/或．醋酸蒸汽及/或．檸檬酸蒸汽。 Notably, other reducing gas systems according to the invention: Nitric oxide. Carbon monoxide and/or. Methane and/or. Hydrogen and/or. Acetic acid vapor and/or. Citric acid steam.
顯著地，發現下列各項用作為惰性氣體：．氙及/或 ．氬及/或．氦及/或．氮及/或．二氧化碳。 Notably, the following items were found to be used as inert gases:. Xenon and/or . Argon and/or. Helium and/or. Nitrogen and/or. carbon dioxide.
在處理腔室中(尤其在一真空中)將基板暴露至電漿。因此，發生氧化物層之一改質。改質藉由氧化物之理想配比之一改變及/或藉由氧化物層厚度至一特定且所要值之消融或藉由氧化物藉由非晶化之一完全移除而發生。 The substrate is exposed to the plasma in the processing chamber, especially in a vacuum. Therefore, one of the oxide layers is modified. Modification occurs by changing one of the ideal ratios of the oxide and/or by ablation of the thickness of the oxide layer to a specific and desired value or by complete removal of the oxide by one of the amorphous.
電漿之離子能量小於1000eV，較佳小於500eV，更佳小於250eV，甚至更佳小於150eV，且最佳在30eV與150eV之間。 The plasma ion energy is less than 1000 eV, preferably less than 500 eV, more preferably less than 250 eV, even more preferably less than 150 eV, and most preferably between 30 eV and 150 eV.
然後，在相同模組中或較佳在尤其經組態用於此目的之一分離結合模組中基板彼此對準且彼此進行接觸。如此一來，基板結合。視需要，可藉由施加一力進一步促進此以確保基板在整個表面上進行可靠接觸。電漿模組與結合模組之間之傳送在高度真空環境中藉由一移動裝置發生。在此處理中，較佳藉由一自動機傳輸基板。 Then, the substrates are aligned and brought into contact with each other in the same module or preferably in a separate bonding module that is especially configured for this purpose. In this way, the substrates are bonded. If necessary, this can be further promoted by applying a force to ensure reliable contact of the substrate on the entire surface. The transmission between the plasma module and the coupling module takes place in a high vacuum environment by a mobile device. In this process, the substrate is preferably transferred by an automaton.
根據本發明，可在兩個基板之結合處理發生之前加工僅一基板之表面或兩個基板之表面。 According to the present invention, the surface of only one substrate or the surfaces of two substrates can be processed before the bonding process of the two substrates occurs.
本發明之優點：．快速，．通用於許多不同基板材料及氧化物類型，．可再生處理結果，．歸因於處理在防止表面之污染之一高度真空中發生之高品質結果，．環境友好的，．經濟的，．無必須處置之廢物，及 ．理想上無(或至少僅一小的或至少可精確調整的)基板表面歸因於植入之損害。 The advantages of the present invention:. fast,. Commonly used in many different substrate materials and oxide types. Renewable processing results,. Due to the high-quality results of the treatment in a high vacuum that prevents contamination of the surface,. Environmentally friendly. Economy,. No waste that must be disposed of, and . Ideally no (or at least only a small or at least precisely adjustable) substrate surface is due to implantation damage.
根據本發明之概念係由在電漿包圍中藉由還原氣體及/或氣體混合物之氧化物之加工(尤其理想配比之精確調整)及/或至少表面附近之一區域中之氧化物之非晶化組成。因此，根據本發明，使用原子及/或分子氣體。 The concept according to the invention consists of the processing of oxides by reducing gases and/or gas mixtures (especially the precise adjustment of the ideal ratio) in the plasma enclosure and/or the non-oxidation of oxides in at least a region near the surface Crystallization composition. Therefore, according to the invention, atomic and/or molecular gases are used.
基本上，本發明係基於在一電漿之一還原氣氛中加工基板。為此目的，可想像由適用於實施結合側上存在之氧化物之氧化物還原之至少一氣體組成之所有氣氛。 Basically, the present invention is based on processing a substrate in a reducing atmosphere in one of the plasmas. For this purpose, all atmospheres consisting of at least one gas suitable for carrying out oxide reduction of oxides present on the bonding side can be imagined.
歸因於其可用性及吸引人的成本，根據本發明較佳使用H2。文獻中已知可藉由使用H2還原半導體基板上之氧化物。然而，作為一規則，此需要一非常高的溫度(>600℃)。此對於大量基板(尤其複合物半導體基板)係不可接受的，其係因為最壞情況下此將導致材料之一分解(例如，GaAs在400℃下分解)，或至少歸因於擴散處理之層結構中之一改變。因此，本發明之一主要態樣係組態處理使得氧化物還原可發生在低溫下，較佳低於200℃，更佳低於150℃，甚至更佳低於100℃，且最佳在室溫下。 Due to its availability and attractive cost, H 2 is preferably used according to the invention. It is known in the literature that oxides on semiconductor substrates can be reduced by using H 2 . However, as a rule, this requires a very high temperature (>600°C). This is unacceptable for a large number of substrates (especially composite semiconductor substrates) because it will cause one of the materials to decompose in the worst case (for example, GaAs decomposes at 400°C), or at least due to the diffusion treatment layer One of the structure changes. Therefore, one of the main aspects of the present invention is that the configuration treatment allows oxide reduction to occur at low temperatures, preferably below 200°C, more preferably below 150°C, even more preferably below 100°C, and is best at room temperature Warm.
為使此可能，自經選擇氣氛點火一電漿。歸因於在電漿中產生且貫在基板上之離子之離子能量，供應或提供足夠能量，使得可在非常低的溫度(較佳室溫)發生反應及/或使得發生氧化物之非晶化。以此方式，可關於熱應力非常輕的加工材料。 To make this possible, a plasma was ignited by choosing the atmosphere. Due to the ion energy of the ions generated in the plasma and passing through the substrate, sufficient energy is supplied or provided so that the reaction can occur at a very low temperature (preferably room temperature) and/or the amorphous oxide Change. In this way, materials with very light thermal stress can be processed.
藉由參數調整，可在無需改變基礎化學之情況下使用相同基本觀念加工多種不同之基板。較佳地，可取決於化學式藉由用於處理腔室之氣體供應系統之部分之一氣體混合系統調整兩個或兩個以上之氣體之氣體混合物；以此方式，可調適氣體混合物用於不同基板。 By adjusting the parameters, a variety of different substrates can be processed using the same basic concept without changing the basic chemistry. Preferably, the gas mixture of two or more gases can be adjusted by a gas mixing system that is part of the gas supply system of the processing chamber depending on the chemical formula; in this way, the gas mixture can be adjusted for different Substrate.
理論上，可想像用於處理之實施之任何類型之電漿腔室。此包 含CCP腔室(英文：「電容耦合電漿」)、ICP腔室(英文：「感應耦合電漿」)，及遠端電漿腔室。 In theory, any type of plasma chamber can be imagined for the implementation of processing. This package Contains CCP chamber (English: "capacitively coupled plasma"), ICP chamber (English: "inductively coupled plasma"), and remote plasma chamber.
根據本發明，CCP腔室歸因於其等簡單結構及高生產力仍係較佳的。電極之間之距離共計大於2mm，較佳大於6mm，甚至更佳大於9mm，甚至更佳大於12mm，且最佳大於16mm。根據本發明，尤其設想將底電極同時實施為一基板固持器。可將此基板固持器同時實施為一真空樣本固持器抑或者且較佳為一靜電樣本固持器。可進一步想像併入允許基板之一(適度)溫度改變之加熱及/或冷卻元件。 According to the present invention, the CCP chamber is still preferred due to its simple structure and high productivity. The total distance between the electrodes is greater than 2mm, preferably greater than 6mm, even more preferably greater than 9mm, even more preferably greater than 12mm, and most preferably greater than 16mm. According to the invention, it is especially envisaged that the bottom electrode is simultaneously implemented as a substrate holder. The substrate holder can be implemented as a vacuum sample holder or, preferably, as an electrostatic sample holder. It is further conceivable to incorporate heating and/or cooling elements that allow a (moderate) temperature change of one of the substrates.
上部電極上之經施加AC電壓之頻率較佳大於下部電極上之經施加AC電壓之頻率。較佳地，該等頻率之間存在至少10之一因數、更佳至少100之一因數且甚至更佳至少250之一因數之一差異。藉此彼此之頻率之一相互影響減小。特定言之，上部頻率可共計13.56MHz或27MHz；而特定言之，下部電極所暴露之頻率可共計40kHz、100kHz，或400kHz。在此配置中，上部頻率主要引起氣氛之一電離，而下部頻率引起離子至基板表面上之加速。因此，電漿之密度及離子藉由其敲擊基板之離子能量係個別可調整的。此係有利的，其係因為由於根據本發明之離子密度與離子能量可彼此分開且獨立地調整，故處理係更可管理的。 The frequency of the applied AC voltage on the upper electrode is preferably greater than the frequency of the applied AC voltage on the lower electrode. Preferably, there is a difference of at least a factor of 10, more preferably a factor of at least 100, and even better a factor of at least 250 between these frequencies. As a result, one of the frequencies of the mutual influence is reduced. In particular, the upper frequency may total 13.56 MHz or 27 MHz; and in particular, the frequency exposed by the lower electrode may total 40 kHz, 100 kHz, or 400 kHz. In this configuration, the upper frequency mainly causes one of the atmosphere to ionize, while the lower frequency causes the acceleration of ions onto the substrate surface. Therefore, the density of the plasma and the ion energy by which it strikes the substrate are individually adjustable. This is advantageous because, because the ion density and ion energy according to the present invention can be adjusted separately and independently from each other, the treatment is more manageable.
在用於Si晶圓之氧化物還原之一較佳組態中，上部電極之AC電壓之頻率共計13.56MHz，且下部電極之AC電壓之頻率共計80kHz與120kHz之間。上部及下部電極之功率位於50W與500W之間。較佳地，將濃度值位於100%H2/0%Ar與0%H2/100%Ar之間且不具有大於1%之其他顯著成分之H2/Ar之一混合物用作為一氣體混合物。濃度較佳低於80%H2，更佳低於60%H2，甚至更佳低於40%H2，且最佳低於20%H2。 In a preferred configuration for oxide reduction of Si wafers, the frequency of the AC voltage of the upper electrode totals 13.56 MHz, and the frequency of the AC voltage of the lower electrode totals between 80 kHz and 120 kHz. The power of the upper and lower electrodes is between 50W and 500W. Preferably, a mixture of H 2 /Ar with a concentration value between 100%H 2 /0%Ar and 0%H 2 /100%Ar and having no other significant components greater than 1% is used as a gas mixture . The concentration is preferably below 80% H 2 , more preferably below 60% H 2 , even more preferably below 40% H 2 , and most preferably below 20% H 2 .
氣體之供應在電漿腔室之周圍均勻地發生以確保一均勻處理結 果。氣體離開電漿腔室之排放尤其藉由分佈在腔室之周圍之出口同樣均勻地發生。在電漿加工處理期間，使用氣體混合物持續充滿腔室以自腔室移除藉由反應產生之反應產物，尤其H2O。由於尤其設想對於較佳氧化物還原，將發生比Si與H2O之重新氧化更大量之還原反應，故此係重要的。為確保反應之均勻性，尤其設想確保處理期間腔室中之一均勻氣體流動及因此處理氣體之一均勻濃度。 The supply of gas occurs uniformly around the plasma chamber to ensure a uniform processing result. The discharge of gas from the plasma chamber especially occurs evenly through outlets distributed around the chamber. During the plasma processing process, the chamber is continuously filled with a gas mixture to remove reaction products generated by the reaction, especially H 2 O, from the chamber. This is important because it is especially envisaged that for better oxide reduction, a larger amount of reduction reaction will occur than the re-oxidation of Si and H 2 O. In order to ensure the uniformity of the reaction, it is especially envisaged to ensure a uniform gas flow in the chamber during the processing and therefore a uniform concentration of the processing gas.
主要經由下部電極控制離子能量，粒子藉由離子能量敲擊基板之表面。一方面，此能量影響基板表面上之氧化物之成功加工；且另一方面，其經設定如此低使得僅發生基板表面之最小植入及相關聯損害。 The ion energy is mainly controlled through the lower electrode, and the particles strike the surface of the substrate with the ion energy. On the one hand, this energy affects the successful processing of oxides on the substrate surface; and on the other hand, it is set so low that only minimal implantation of the substrate surface and associated damage occurs.
然而，另一方面，可期望產生基板表面之一受控之損害以產生具有一較低機械強度之一層。此藉由基於一高按壓力之按壓在基板進行接觸之後有利地實現表面之間之奈米間隙之密貼。表面上之壓力在0.01MPa與10MPa之間，較佳在0.1MPa與8MPa之間，更佳在1MPa與5MPa之間，且最佳在1.5MPa與3MPa之間。對於一普通200mm基板此等值大致對應於自1kN至320kN之一力衝擊。較佳地且根據本發明，氧化物或至少表面附近之氧化物區域之一非晶化藉由此受控之損害發生。表面之非晶化較佳藉由離子能量之調整發生。非晶區域可包括整個氧化物層，但較佳限於一表面附近區域。特定言之，非晶層之厚度藉此小於10nm，較佳小於5nm，更佳小於1nm，且最佳小於0.1nm。 However, on the other hand, it may be desirable to produce controlled damage to one of the substrate surfaces to produce a layer with a lower mechanical strength. This advantageously achieves the adhesion of the nano-gap between the surfaces after the substrates are brought into contact by pressing based on a high pressing force. The pressure on the surface is between 0.01 MPa and 10 MPa, preferably between 0.1 MPa and 8 MPa, more preferably between 1 MPa and 5 MPa, and most preferably between 1.5 MPa and 3 MPa. For a common 200mm substrate, this value roughly corresponds to a force impact from 1kN to 320kN. Preferably and according to the invention, amorphization of the oxide or at least one of the oxide regions near the surface occurs by controlled damage. Amorphization of the surface preferably occurs by adjustment of ion energy. The amorphous region may include the entire oxide layer, but is preferably limited to a region near a surface. In particular, the thickness of the amorphous layer is thereby less than 10 nm, preferably less than 5 nm, more preferably less than 1 nm, and most preferably less than 0.1 nm.
較佳地，可想像首先藉由經最佳化用於氧化物還原之一氣體混合物開始處理，且在氧化物還原發生之後改變氣體混合物且轉變成經最佳化用於目標表面損害之一混合物。此可在處理期間動態地發生且可藉由一控制裝置(尤其一經軟體支援之控制裝置)實施。 Preferably, it is conceivable that the treatment is first started by optimizing a gas mixture for oxide reduction, and after the oxide reduction occurs, the gas mixture is changed and converted to a mixture optimized for target surface damage . This can happen dynamically during processing and can be implemented by a control device, in particular a control device supported by software.
亦可藉由用於上部及/或下部電極之頻率產生器之調整之一調適 完成改變氣體混合物。以此方式，可較佳地調整下部及/或上部頻率產生器之功率、變更用於產生器之電壓及電流值，且改變頻率。此繼而可由控制裝置動態地實施。藉由此等參數，可調整經損害層之厚度、損害之密度，及視需要經植入離子之種類或劑量。 It can also be adjusted by one of the adjustments of the frequency generator for the upper and/or lower electrodes Finish changing the gas mixture. In this way, it is possible to better adjust the power of the lower and/or upper frequency generator, change the voltage and current values used for the generator, and change the frequency. This can then be implemented dynamically by the control device. With these parameters, the thickness of the damaged layer, the density of the damage, and the type or dose of implanted ions can be adjusted as needed.
損害通常與表面附近區域之一非晶化相關聯。 The damage is usually associated with amorphization in one of the areas near the surface.
作為一規則，在自半導體基板移除氧化物之情況下，藉由還原暴露位於下方且係單晶或至少結晶(歸因於MO CVD，具有少數缺陷(例如，生長缺陷))之半導體晶圓。 As a rule, in the case of removing the oxide from the semiconductor substrate, the semiconductor wafer that is underneath by reduction and is single crystal or at least crystalline (due to MO CVD, with few defects (eg, growth defects)) is exposed .
因此，一典型處理序列在於將一基板裝載至用於結合層之至少一者之一改質之一電漿腔室中、氧化物還原、氧化物還原處理，及視需要用於基板之最上層之目標改質/損害之一處理。 Therefore, a typical processing sequence consists of loading a substrate into a plasma chamber for modification of at least one of the bonding layers, oxide reduction, oxide reduction processing, and if necessary for the uppermost layer of the substrate One of the target modification/damage treatment.
此外，在工作空間內部在一高度真空環境中將基板傳輸至一結合腔室且在該處將其等機械及/或光學地對準且進行接觸。視需要，亦將其等暴露至一(重)力且按壓在一起。隨後可移除基板上之壓力。根據本發明，結合腔室可與電漿腔室相同，即一結合電漿腔室。 In addition, the substrate is transferred to a bonding chamber in a high vacuum environment inside the work space and is mechanically and/or optically aligned and contacted there. If necessary, they are also exposed to a (heavy) force and pressed together. The pressure on the substrate can then be removed. According to the present invention, the bonding chamber may be the same as the plasma chamber, that is, a bonding plasma chamber.
根據本發明，高度真空環境具有小於1x10-5毫巴、較佳小於5x10-6毫巴、更佳小於1x10-6毫巴、甚至更佳小於5x10-7毫巴且最佳小於9x10-8毫巴之一壓力。 According to the invention, the high vacuum environment has less than 1x10 -5 mbar, preferably less than 5x10 -6 mbar, more preferably less than 1x10 -6 mbar, even more preferably less than 5x10 -7 mbar and most preferably less than 9x10 -8 mbar Pakistani one pressure.
在另一組態中，根據本發明之還原處理不用於氧化物之完全移除，而用於設定氧化物之一正確理想配比。特定言之，可藉此產生具有結合氧之剩餘之一元素/若干元素之層。例如，發現氧化矽不係理想配比正確形式，如SiO2，而係如非理想配比之SiO2-x。一般而言，(例如)產生其中x在0與2之間之非理想配比組合物SiO2-x。類似考量適用於其他氧化物。在結晶物理學方面非理想配比應被理解為歸因於氧原子在晶格中不存在於其等之位置。歸因於氧原子之此不存在，缺陷之密度增大。繼而缺陷對於所有類型之傳輸處理極度重要。 In another configuration, the reduction process according to the present invention is not used for the complete removal of oxides, but for setting one of the correct ideal ratios of oxides. In particular, a layer with the remaining element/elements combined with oxygen can be produced thereby. For example, it is found that silicon oxide is not the correct form of ideal ratio, such as SiO 2 , but is not SiO 2-x of non-ideal ratio. In general, for example, a non-ideal composition SiO 2-x where x is between 0 and 2 is produced. Similar considerations apply to other oxides. The non-ideal ratio in crystal physics should be understood to be due to the absence of oxygen atoms at their equivalent positions in the crystal lattice. Due to the absence of oxygen atoms, the density of defects increases. In turn, defects are extremely important for all types of transmission processing.
在另一組態中，根據本發明之還原處理不用於氧化物之完全移除，而用於產生具有一經界定層厚度之氧化物層。藉此，藉由根據本發明之還原處理消融已存在之氧化物層以達到一所要厚度。接著可將如此產生之層(例如)用於專利PCT/EP2011/000299、PCT/EP2011/055470、PCT/EP2011/055469及PCT/EP2011/055471中揭示之處理。根據本發明，在移除處理之前氧化物大於1nm，較佳大於100nm，更佳大於10μm，甚至更佳大於100μm，且最佳大於1000μm。在移除處理之後，氧化物較佳小於100μm，較佳小於10μm，更佳小於100nm，甚至更佳小於10nm，且最佳小於1nm。 In another configuration, the reduction process according to the present invention is not used for the complete removal of the oxide, but for producing an oxide layer with a defined layer thickness. Thereby, the existing oxide layer is ablated by the reduction process according to the present invention to achieve a desired thickness. The layers so produced can then be used, for example, for the processes disclosed in patents PCT/EP2011/000299, PCT/EP2011/055470, PCT/EP2011/055469, and PCT/EP2011/055471. According to the invention, the oxide before removal is greater than 1 nm, preferably greater than 100 nm, more preferably greater than 10 μm, even more preferably greater than 100 μm, and most preferably greater than 1000 μm. After the removal process, the oxide is preferably less than 100 μm, preferably less than 10 μm, more preferably less than 100 nm, even more preferably less than 10 nm, and most preferably less than 1 nm.
氧化物層之目標改質幫助產生一最佳混合結合。一混合結合係繼而由導電及非導電區域組成之兩個表面之間之一連接。導電區域主要係金屬區域(尤其由銅製成)，而非導電區域主要由一介電質(諸如，氧化矽)組成。介電質區域與電區域尤其向下接地至相同水平面，使得電區域完全由一介電質圍繞且因此與環境絕緣。藉由兩個此等混合表面之對準及接觸及結合，形成一混合結合，即其上較佳導電區域與非導電區域彼此結合之兩個基板之間之一連接。 The targeted modification of the oxide layer helps to produce an optimal hybrid bond. A hybrid bond is then a connection between two surfaces composed of conductive and non-conductive regions. The conductive area is mainly a metal area (especially made of copper), while the non-conductive area is mainly composed of a dielectric substance (such as silicon oxide). The dielectric area and the electrical area are especially grounded down to the same level, so that the electrical area is completely surrounded by a dielectric and is therefore insulated from the environment. By aligning, contacting, and bonding the two such hybrid surfaces, a hybrid bond is formed, that is, one of the two substrates on which the conductive region and the non-conductive region are bonded to each other is connected.
尤其，根據本發明之基板係其中結合側上存在Cu-Cu結合之Si基板，其在處理之進一步進程中被結合。或者，可使用根據本發明之具有其他金屬層(諸如，Au、W、Ni、Pd、Pt、Sn等)或金屬之一組合之基板。此之實例係塗覆有Al之Si晶圓、塗覆有Cu及Sn之Si晶圓、塗覆有Ti之Si晶圓，或覆蓋有Cu及意欲防止Cu擴散至Si中之(例如)Ti、Ta、W、TiN、TaN、TiW等之一工業標準障壁層(在Cu下方且為熟悉此項技術者所知曉)之Si基板。此等擴散障壁係熟悉此項技術者所知曉的。 In particular, the substrate according to the present invention is a Si substrate in which there is Cu-Cu bonding on the bonding side, which is bonded in a further process of processing. Alternatively, a substrate having a combination of other metal layers (such as Au, W, Ni, Pd, Pt, Sn, etc.) or one of metals according to the present invention may be used. Examples of this are Si wafers coated with Al, Si wafers coated with Cu and Sn, Si wafers coated with Ti, or Ti covered with Cu and intended to prevent Cu from diffusing into Si (for example) Ti , Ta, W, TiN, TaN, TiW and other industry standard barrier layer (under Cu and known to those skilled in the art) Si substrate. These diffusion barriers are known to those skilled in the art.
因此，根據本發明，提供可密封(較佳密閉)且可鎖定以隔絕環境(意謂一氧化氣氛)之一工作空間且提供其中可發生結合側(較佳整個基 板上)上之潛在氧化物層之一還原且結合兩者之適當附接模組係重要的。藉此可防止還原處理與結合處理之間之結合側之一重新氧化。取決於基板(尤其基板上之金屬塗層)之狀態，一氣氛之不同成分可係氧化的。然而，在多數情況下，氧及含有氧之化學化合物具有一氧化作用。因此，在工作空間中，在使用一還原介質組合物時應大幅降低氧及水分/水蒸氣之濃度(或較佳接近0)。工作空間連接多個模組，使得可能在模組群之模組之間傳輸基板而不將基板再暴露至氣氛。可想像其中僅一模組連接至工作空間之組態；然而，此模組可執行根據本發明之所有需要任務。在此情況下，工作空間專門用於裝載及卸載。 Therefore, according to the present invention, a working space that is sealable (preferably airtight) and lockable to isolate the environment (meaning an oxidizing atmosphere) is provided and a bonding side (preferably the entire base) where the bonding can occur It is important that one of the potential oxide layers on the board) be restored and a proper attachment module combining the two. This prevents one of the bonding sides between the reduction process and the bonding process from being re-oxidized. Depending on the state of the substrate (especially the metal coating on the substrate), different components of an atmosphere can be oxidized. However, in most cases, oxygen and chemical compounds containing oxygen have an oxidizing effect. Therefore, in the working space, the concentration of oxygen and water/water vapor should be greatly reduced (or preferably close to 0) when using a reducing medium composition. The working space connects multiple modules, making it possible to transfer the substrate between the modules of the module group without exposing the substrate to the atmosphere. One can imagine a configuration in which only one module is connected to the workspace; however, this module can perform all the required tasks according to the present invention. In this case, the workspace is dedicated to loading and unloading.
根據本發明，尤其可想像將額外模組連接至工作空間以用於進一步處理最佳化，尤其用於待在工作空間中結合之基板之物理及/或化學特性之預及/或後加工及/或量測。此處主要程序步驟可係加熱、還原、對準、冷卻、厚度量測、結合強度量測等。 According to the invention, it is especially conceivable to connect additional modules to the workspace for further processing optimization, especially for the pre- and/or post-processing of the physical and/or chemical properties of the substrate to be combined in the workspace /Or measurement. The main program steps here can be heating, reduction, alignment, cooling, thickness measurement, bonding strength measurement, etc.
根據本發明，在根據本發明之額外模組(諸如，尤其還原模組及結合模組)配置在工作空間周圍(尤其移動機構周圍)時，此在硬體方面可尤其有利地進行，藉此模組尤其可停駐在工作空間上。移動機構較佳係具有對應端接器之一行業標準工業自動機。藉此，模組可繞中心模組尤其以一星狀或簇狀配置或停駐。 According to the invention, when additional modules according to the invention (such as, in particular, the reduction module and the combination module) are arranged around the working space (especially around the moving mechanism), this can be performed particularly advantageously in terms of hardware, thereby In particular, the module can be parked on the work space. The mobile mechanism is preferably an industry standard industrial automaton with one of the corresponding terminators. In this way, the modules can be arranged or parked in a star or cluster shape, especially around the central module.
在最理想情況下，還原模組及結合模組經構造使得整個系統關於此等處理步驟之產量最大化。 In the most ideal case, the reduction module and the combination module are constructed to maximize the output of the entire system with respect to these processing steps.
在一尤其有利組態中，其中至少一者係一還原模組且第二者係一類型之儲存模組之至少兩個模組將位於結合模組之前。將裝載有晶圓之結合卡盤裝載至還原模組中且進行加工。之後可將結合卡盤初始儲存在儲存模組中，使得其等可在任何時間立即用於結合。在一特殊組態中，亦可將儲存模組構造為一還原模組。還原模組較佳經構造使得可同時接受多個結合卡盤及/或多個基板。 In a particularly advantageous configuration, at least one of which is a restore module and the second is at least two modules of a type of storage module will be located before the combined module. The combined chuck loaded with wafers is loaded into the reduction module and processed. After that, the combination chuck can be initially stored in the storage module, so that it can be used for combination immediately at any time. In a special configuration, the storage module can also be constructed as a restore module. The reduction module is preferably constructed such that it can simultaneously receive multiple bonding chucks and/or multiple substrates.
本發明之一尤其獨立態樣係可如何以一導電且光學透明形式藉由同時經濟的一處理堆疊此等層。此外，描述此需要之基板之準備。 One particularly independent aspect of the invention is how these layers can be stacked in a conductive and optically transparent form by a simultaneous economical process. In addition, the preparation of the required substrate is described.
藉此，所描述方法較佳適用於堆疊多層太陽能電池。或者，該方法亦可經實施以產生其中需要任意(尤其光學)材料(尤其半導體材料、玻璃，及陶瓷)之間之光學透明且導電連接之所有其他結構及組件。在此片段中，歸因於固體光源(諸如，LED及雷射)在各種應用(諸如，照明、通信，及材料加工)中之大幅增加之重要性，出現增加量之使用。同樣在顯示器製造之片段中，由於諸如觸控偵測(觸控螢幕之領域中之反饋，等)之額外功能被整合至顯示器中，故新且創新的製造技術變得更重要。 In this way, the described method is preferably suitable for stacking multilayer solar cells. Alternatively, the method can also be implemented to produce all other structures and components in which optically transparent and electrically conductive connections between any (especially optical) materials (especially semiconductor materials, glass, and ceramics) are required. In this segment, due to the significant increase in the importance of solid-state light sources (such as LEDs and lasers) in various applications (such as lighting, communications, and material processing), there has been an increased amount of use. Also in the display manufacturing segment, as additional functions such as touch detection (feedback in the field of touch screens, etc.) are integrated into the display, new and innovative manufacturing technologies become more important.
本發明之優點尤其係：- 導電、光學透明的結合介面或化合物層，- 非常薄、強健，且長期穩定的結合介面或層，- 耐熱的結合介面或層及- 高效率(快速且經濟之生產)。 The advantages of the present invention are in particular:-conductive, optically transparent bonding interface or compound layer,-very thin, strong, and long-term stable bonding interface or layer,-heat-resistant bonding interface or layer and-high efficiency (fast and economical produce).
本發明之一中心(尤其獨立)態樣係使用透明導電氧化物在基板之間製造導電且光學透明的化合物層。尤其藉由晶圓結合、較佳藉由一直接結合處理且更佳藉由使用電漿活化之一直接結合處理產生該化合物。 One of the central (especially independent) aspects of the invention is the use of transparent conductive oxides to produce conductive and optically transparent compound layers between substrates. The compound is produced particularly by wafer bonding, preferably by a direct bonding process and more preferably by using a direct plasma bonding process.
銦錫氧化物(簡稱「ITO」)尤其用於透明、導電的氧化物(英文：「透明導電氧化物」，或簡稱「TCO」)。此後ITO將用作為銦錫氧化物之縮寫。ITO廣泛用於LCD顯示器之製造中，其中其用作為一光學透明電導體。或者，使用下列材料：- 經摻雜氧化鋅，尤其摻雜鋁之氧化鋅(簡稱「AZO」)、摻雜鎵之氧化鋅(簡稱「GZO」)。 Indium tin oxide (referred to as "ITO") is especially used for transparent, conductive oxides (English: "transparent conductive oxide", or "TCO" for short). Hereinafter ITO will be used as an abbreviation for indium tin oxide. ITO is widely used in the manufacture of LCD displays, where it is used as an optically transparent electrical conductor. Alternatively, the following materials are used:-Zinc oxide doped with zinc, especially aluminum-doped zinc oxide (referred to as "AZO"), gallium-doped zinc oxide (referred to as "GZO").
- 摻雜氟化物之氧化錫(英文：「氟氧化錫」或簡稱「FTO」)，及 - 銻氧化錫(簡稱「ATO」)。 -Fluoride-doped tin oxide (English: "Fluorine Tin Oxide" or "FTO" for short), and -Antimony tin oxide (referred to as "ATO").
基本上，可使用係可氧化且藉由對應摻雜具有所要特性(尤其導電率及光學透明性)之任何材料。 Basically, any material that can be oxidized and has the desired characteristics (especially conductivity and optical transparency) by corresponding doping can be used.
根據本發明，導電率係用於材料具有>10e1S/cm(較佳10e2S/cm，且更佳>10e3S/cm)之一導電率(藉由半導體技術中標準之四點方法量測，且其關於300K之一溫度)時之此方面之術語。被定義為一特定波長範圍之光應穿過典型使用期間之層之百分比之光學透射(穿透因數)透過具有典型厚度之一膜應共計至少>80%，較佳>87%，更佳>93%，且甚至更佳>96%。 According to the present invention, conductivity is used for materials having a conductivity of >10e1S/cm (preferably 10e2S/cm, and more preferably >10e3S/cm) (measured by a standard four-point method in semiconductor technology, and With regard to a temperature of 300K)). The optical transmission (transmittance factor) defined as the percentage of light in a specific wavelength range that should pass through a layer during typical use should pass through a film with a typical thickness of at least >80%, preferably >87%, more preferably> 93%, and even better >96%.
根據本發明，自300nm延伸至1800nm之波長範圍較佳用於光伏打用途。其意謂相關波長範圍以任何比率大於人類可見之波長範圍。此應確保可將光之UV部分及光之IR部分轉換成電能。因為一多層太陽能電池之最上層已處理光譜之一部分且因此將其轉換成電能，所以若結合連接具有其中其容許透射之一某種程度上較小的波長範圍，則可接受。特定言之，因此上文給定之透射值應施加至至少>600nm、較佳>500nm、更佳>400nm且最佳>350nm之波長。此外，透射值亦應施加至自最小波長開始至1300nm之一最大值、較佳至1500nm之一最大值、更佳至1700nm之一最大值且最佳至1800nm之一最大值之整個波長範圍。 According to the invention, the wavelength range extending from 300 nm to 1800 nm is preferably used for photovoltaic applications. It means that the relevant wavelength range is greater than the wavelength range visible to humans at any ratio. This should ensure that the UV part of the light and the IR part of the light can be converted into electrical energy. Because the uppermost layer of a multi-layer solar cell has processed a portion of the spectrum and therefore converted it into electrical energy, it is acceptable if the bonding connection has a somewhat smaller wavelength range in which it allows transmission. In particular, the transmission values given above should therefore be applied to wavelengths of at least >600 nm, preferably >500 nm, more preferably >400 nm and most preferably >350 nm. In addition, the transmission value should also be applied to the entire wavelength range from the minimum wavelength to a maximum value of 1300 nm, preferably to a maximum value of 1500 nm, more preferably to a maximum value of 1700 nm and optimally to a maximum value of 1800 nm.
根據本發明，尤其藉由以下方法將氧化物施加至待結合之基板：- MO CVD，金屬有機分子光束沈積，- 噴霧熱解、脈衝雷射沈積(PLD)或，- 濺射。 According to the invention, the oxide is applied to the substrate to be bonded in particular by the following methods:-MO CVD, metal organic molecular beam deposition,-spray pyrolysis, pulsed laser deposition (PLD) or,-sputtering.
為確保層之所要特性，根據本發明，確保正確混合物比率係重要的。特定言之，氧之量可藉由此等氧化物之一些改良光學透明性， 藉此必須確保氧之量不會太高，否則將減小導電率。 To ensure the desired properties of the layer, according to the invention, it is important to ensure the correct mixture ratio. In particular, the amount of oxygen can improve the optical transparency by some of these oxides, This must ensure that the amount of oxygen is not too high, otherwise the conductivity will be reduced.
一般而言，藉由沈積在待結合基板上之一前驅體層結構產生結合連接(化合物層，亦為結合介面)。隨後，電漿活化且尤其在室溫下接合該等層，藉此引起一預結合(暫時結合)。在此後之加熱加工處理(退火)期間，將前驅體層結構轉換成由透明、導電氧化物組成之一層，藉此同時強化結合連接。至少存在於表面區域中之一非晶層可影響結合處理，其尤其有利。藉由施加一適當力，可確保表面附近區域之變形，其保證微小及/或奈米細孔之最佳密封。 Generally speaking, a bonding connection (compound layer, also a bonding interface) is generated by a precursor layer structure deposited on the substrate to be bonded. Subsequently, the plasma is activated and the layers are joined especially at room temperature, thereby causing a pre-bonding (temporary bonding). During the subsequent heat processing (annealing), the precursor layer structure is converted into a layer composed of transparent, conductive oxide, thereby simultaneously strengthening the bonding connection. At least one amorphous layer present in the surface area can affect the bonding process, which is particularly advantageous. By applying an appropriate force, the deformation of the area near the surface can be ensured, which guarantees the optimal sealing of tiny and/or nanopores.
在使用成形氣體時，應注意可能藉由基於濺射及氧化物還原之一處理變更且尤其完全移除氧化物層。 When using forming gas, it should be noted that the oxide layer may be modified and especially completely removed by one of the processes based on sputtering and oxide reduction.
或者或除此方法之外，根據本發明，將變更氧化物層與進行接觸之間之時間最小化至尤其<2小時、較佳<30分鐘、更佳<15分鐘且理想上<5分鐘係有利的。藉此，可最小化氧化物層之目標調整之後之一非所要且變更之氧化物生長。 Or or in addition to this method, according to the invention, the time between changing the oxide layer and making contact is minimized to especially <2 hours, preferably <30 minutes, more preferably <15 minutes and ideally <5 minutes advantageous. In this way, an undesired and altered oxide growth after the target adjustment of the oxide layer can be minimized.
藉由在真空腔室中設定一特定壓力，可想像影響或調整用於根據本發明之電漿離子之平均自由徑長度。 By setting a specific pressure in the vacuum chamber, it is conceivable to influence or adjust the average free path length for plasma ions according to the present invention.
在電容耦合之情況，將電極配置在電漿腔室內部係有利的。 In the case of capacitive coupling, it is advantageous to arrange the electrodes inside the plasma chamber.
藉由電極之(不同)頻率、振幅、尤其且較佳專門施加至第二電極之一偏壓電壓及腔室壓力之參數之調整達到接觸表面之一最佳敲擊。 By adjusting the (different) frequency, amplitude of the electrode, and particularly and preferably the parameters of the bias voltage and the chamber pressure applied specifically to one of the second electrodes, an optimal tapping of the contact surface is achieved.
將電漿活化系統設計為一電容耦合之雙頻電漿系統有利地使得可能分開調整至晶圓表面上之離子之離子密度及加速度。因此，可在一廣泛窗口內調整且可調適可獲得之處理結果以滿足使用要求。 Designing the plasma activation system as a capacitively coupled dual frequency plasma system advantageously makes it possible to separately adjust the ion density and acceleration of ions on the wafer surface. Therefore, it is possible to adjust within a wide window and adapt the available processing results to meet the requirements of use.
尤其第二(特定言之，下部)電極之一基本電壓之形式之偏壓電壓用以影響(且尤其減小或加速)至裝納在第二電極上之基板之接觸表面上之電極之衝擊(速度)。 In particular, the bias voltage in the form of a basic voltage of the second (specifically, lower) electrode is used to influence (and especially reduce or accelerate) the impact to the electrode on the contact surface of the substrate mounted on the second electrode (speed).
藉由上述參數，可調整尤其非晶層之品質，藉此此後將描述尤 其有利組態。 With the above parameters, the quality of the particularly amorphous layer can be adjusted, whereby Its favorable configuration.
藉由一感應耦合電漿源，可將關於電容耦合之AC電壓之對應類比考量應用於用以產生一磁場之交流電。根據本發明，可想像藉由一交流電AC或改變強度及/或頻率之磁場操縱感應耦合電漿源之電漿，使得電漿具有根據本發明之對應特性。 With an inductively coupled plasma source, the corresponding analogous considerations regarding the capacitively coupled AC voltage can be applied to the alternating current used to generate a magnetic field. According to the present invention, it is conceivable that the plasma of an inductively coupled plasma source is manipulated by an alternating current AC or a magnetic field of varying strength and/or frequency so that the plasma has the corresponding characteristics according to the present invention.
藉由一遠端電漿，在一外部源中產生待使用之實際電漿且將其引入至樣本腔室中。特定言之，將此電漿之成分(尤其離子)傳輸至樣本腔室中。可藉由各種元件(諸如，水閘、加速器、磁及/或電透鏡、混合物等)確保電漿自源腔室至基板腔室之轉移。應將關於電及/或磁場之頻率及/或強度之應用於電容及/或感應耦合電漿之所有考量應用於所有元件，其等確保電漿之產生及/或電漿自源腔室至基板腔室之轉移。例如，可想像一電漿藉由電容或感應耦合及根據本發明之參數產生在源腔室中且隨後經由上述提及之元件進入基板腔室。 With a remote plasma, the actual plasma to be used is generated in an external source and introduced into the sample chamber. In particular, the components (especially ions) of this plasma are transferred into the sample chamber. The transfer of plasma from the source chamber to the substrate chamber can be ensured by various elements (such as water gates, accelerators, magnetic and/or electric lenses, mixtures, etc.). All considerations regarding the frequency and/or strength of electric and/or magnetic fields applied to capacitive and/or inductively coupled plasmas should be applied to all components, etc., to ensure the generation of plasma and/or plasma from the source chamber to Transfer of substrate chamber. For example, it is conceivable that a plasma is generated in the source chamber by capacitive or inductive coupling and parameters according to the present invention and then enters the substrate chamber via the above-mentioned elements.
根據本發明之一進一步有利組態，設想不可逆結合之構造將發生在通常低於300℃、有利地低於200℃、更有利地低於150℃、甚至更有利地低於100℃之一溫度下，且最有利地在室溫下，尤其達12日之一最大值，較佳1日，更佳1小時，且最佳15分鐘。一進一步有利加熱加工方法係藉由微波加熱。 According to a further advantageous configuration of one of the inventions, it is envisaged that the construction of irreversible bonding will occur at a temperature generally below 300°C, advantageously below 200°C, more advantageously below 150°C, even more advantageously below 100°C And most advantageously at room temperature, especially up to a maximum of 12 days, preferably 1 day, more preferably 1 hour, and most preferably 15 minutes. A further advantageous heat processing method is by microwave heating.
藉此在不可逆結合具有大於1.5J/m2、尤其大於2J/m2、較佳大於2.5J/m2之一結合強度時，尤其有利。 Whereby when the irreversible binding of greater than 1.5J / m 2, especially greater than 2J / m 2, preferably greater than one 2.5J / m 2 bond strength, is particularly advantageous.
藉由光伏打系統使用太陽能之重要性增加，其係因為化石燃料在中期正變得缺少；此外，其等提取及使用造成一相當大生態問題，尤其助長溫室效應。自一純經濟立場，為增大光伏打之競爭性，需要在相同成本或至多一適度價格增大下改良將光轉換成電能之效率。然而，如此一來，存在對可能效率之限制。存在此等限制主要係因為一單一半導體材料僅可在一有限波長範圍中處理光且將其轉換成電能。 The importance of using solar energy through photovoltaic systems is increasing because fossil fuels are becoming scarce in the medium term; in addition, their extraction and use cause a considerable ecological problem, especially contributing to the greenhouse effect. From a pure economic standpoint, in order to increase the competitiveness of photovoltaics, it is necessary to improve the efficiency of converting light into electrical energy at the same cost or at most a moderate price increase. However, as a result, there are limits to possible efficiency. These limitations exist mainly because a single semiconductor material can only process light in a limited wavelength range and convert it into electrical energy.
因此，在產生多層太陽能電池或已知在「多接面太陽能電池」下使用本發明尤其有利。 Therefore, it is particularly advantageous to use the present invention under the production of multilayer solar cells or known as "multi-junction solar cells".
在此等中，個別層在太陽能電池中垂直堆疊在彼此之頂部上。入射光首先撞上經最佳化以將具有一特定第一波長範圍之光轉換成電能之最上層。具有大部分不可在此層中處理之一波長範圍之光穿透第一層且打擊經最佳化以處理一第二波長範圍且藉此產生電能之下層第二層。視需要，在此等多層電池中具有大部分不可在此第二層中處理之一波長範圍之光可能打擊經最佳化以處理具有一第三波長範圍之光且將其轉換成電能之一下層第三層。可想像，僅理論上大量之此等層係可能的。在實踐中，以使得入射光首先穿透至其中之最上層處理具有最短波長之波長範圍之一方式構造此等電池。第二層處理其次最短波長範圍，等等。藉此，根據本發明，不僅可想像一兩層結構；實情係，可能三或多層。藉此，計劃光學透明及導電地(意謂盡可能具有小的電阻)將層彼此連接。藉此尤其藉由所謂的「金屬有機化學氣相沈積」處理(簡稱「MO CVD」)發生層之沈積，藉此尤其「就地」(意謂在沈積處理之間不將基板暴露至正常環境氣氛)發生多電池之兩個主動層之沈積。較佳地，改良所得電池之品質之障壁層(第二或第四氧化物層)及/或緩衝層(第二或第四氧化物層)***在主動層之間。 In these, individual layers are stacked vertically on top of each other in solar cells. The incident light first hits the uppermost layer that is optimized to convert light with a specific first wavelength range into electrical energy. Light with a wavelength range that is largely unmanageable in this layer penetrates the first layer and the strike is optimized to process a second wavelength range and thereby generate electrical energy to the lower second layer. If necessary, most of these multi-layer batteries have a wavelength range that cannot be processed in this second layer, which may be optimized to process light with a third wavelength range and convert it into electrical energy. The third layer. It is conceivable that only a large number of these layers are theoretically possible. In practice, these cells are constructed in such a way that the incident light first penetrates into the uppermost layer to process one of the wavelength ranges with the shortest wavelength. The second layer deals with the next shortest wavelength range, and so on. Thus, according to the present invention, not only can one imagine a two-layer structure; in fact, it may be three or more layers. With this, it is planned to connect the layers to each other optically transparent and electrically conductive (meaning as small a resistance as possible). In this way, the deposition of layers occurs in particular by the so-called "metal organic chemical vapor deposition" process (referred to as "MO CVD"), thereby in particular "in situ" (meaning that the substrate is not exposed to the normal environment between deposition processes Atmosphere) The deposition of two active layers of a multi-cell occurs. Preferably, a barrier layer (second or fourth oxide layer) and/or a buffer layer (second or fourth oxide layer) to improve the quality of the resulting battery are interposed between the active layers.
應將下列圖式描述中可用及/或揭示之裝置特徵視為經揭示方法特徵，反之亦然。 The device features available and/or disclosed in the following graphical description should be considered as disclosed method features and vice versa.
圖式中展示(根據本發明之組態)具有對應地識別此等之參考之本發明之優點及特徵，藉此使用相同參考表示具有相同或等效功能之組件或特徵。 The drawing shows (configuration according to the invention) the advantages and features of the invention with correspondingly identifying these references, whereby the same reference is used to denote components or features having the same or equivalent functions.
在圖2中所示之一第一組態中，一電漿腔室4及一結合腔室5係附接(尤其密封)至藉由一工作腔室7界定之一抽真空工作空間22之一模組群3之兩個獨立模組。可尤其藉由一軟體支援之控制裝置控制將工作腔室7抽空至一高度真空。在工作腔室7之內部，尤其提供用於任務之一自動機6在一負載模組8、電漿腔室4及結合腔室5之間傳輸基板1。
In a first configuration shown in FIG. 2, a plasma chamber 4 and a
在根據本發明之一第二組態中，電漿腔室4及結合腔室5合併成一單個模組，即一結合/電漿腔室20。自動機6將基板1自儲存容器8傳輸至結合/電漿腔室20中。
In a second configuration according to the invention, the plasma chamber 4 and the
在根據本發明之一第三組態中，模組群3之一或多個電漿模組4或結合模組5或結合/電漿模組20附接至工作腔室7，此等尤其一起形
成工作空間22。自動機6將基板1自儲存容器8傳輸至電漿模組4及/或結合模組5及/或結合/電漿模組20，尤其亦在此等之間來回。根據本發明，由於使用若干電漿模組4及/或若干結合模組5及/或若干結合/電漿模組20，故實現較高產量。藉由控制裝置控制處理。
In a third configuration according to the present invention, one or more of the plasma modules 4 or the
在根據本發明之一第一處理中，藉由自動機6自儲存容器8移除具有形成於一結合側1o上之氧化物層2(圖1a)之一基板1。
In a first process according to the present invention, a
可將基板1安裝在一機動樣本固持器上且因此在電漿模組4及/或結合模組5及/或結合/電漿模組20之間往復傳輸。必然可在甚至無機動樣本固持器之情況下傳輸基板1。在此情況下，基板1位於已在(尤其內建於)電漿模組4及/或結合模組5及/或結合/電漿模組20中之樣本固持器15。
The
自動機6初始將基板1傳輸至一電漿模組4中。電漿模組4具有一氣體供應器11(尤其裝備有分佈在上部周圍之多個開口)及一出口12(尤其裝備有分佈在下部周圍之多個開口)。藉由氣體供應器11將具有根據本發明之還原氣體之氣體混合物引入至電漿腔室4中。
The
隨後在一下部電極9與一上部電極10之間發生電漿之點火及/或固持。基板1較佳直接位於電極上。若基板1將位於樣本固持器15上，則根據本發明必須將樣本固持器15設計為一電極9。
Then ignition and/or holding of the plasma occurs between a
較佳藉由一出口12自電漿腔室4(尤其持續)移除還原產物。氧化物層2之根據本發明之處理步驟之一者因此發生在電漿模組4中。
The reduction product is preferably removed from the plasma chamber 4 (especially continuously) through an
在根據本發明之一第一變體中，藉由電漿13將氧化物層2轉換成以不同於氧化物層2之一理想配比為特徵之氧化物層2'(圖1b)。在此情況下可早在氧化物之沈積時已藉由缺氧而產生不同理想配比。否則，可藉由電漿通過處理參數之一目標選擇調整及/或至少改變理想配比。
In a first variant according to the invention, the
在一第二變體中，藉由電漿13中之還原氣體將具有一初始層厚
度d之氧化物層2薄化至具有一最終層厚度d'之氧化物層2"(圖1c)。
In a second variant, the reducing gas in the
在一第三變體中，發生氧化物層2之完全移除(圖1d)。
In a third variant, a complete removal of the
較佳藉由具有一源18及一偵測器19(較佳就地可檢查氧化物層2、2'、2"之表面2o)之一源偵測器系統發生氧化物2、2'、2"之條件之監測。源18及/或偵測器19可在電漿腔室4之內部及/或外部。若其等在外部，則其等較佳藉由凸緣17真空密連接至電漿腔室4。源偵測器系統可使用適用於提供關於氧化物層2、2'、2"之條件之資訊之任何已知物理量測原理。此等資訊係氧化物層2、2'、2"之厚度、孔隙率，及因此密度及反射率。
The
較佳地，使用橢偏計或衍射計；在特殊情況下，使用反射率計。 Preferably, an ellipsometer or diffractometer is used; in special cases, a reflectometer is used.
經如此處理之第一基板1尤其儲存在配置在工作空間22中之儲存容器(未展示)中。
The
將同樣依據根據本發明之處理在其結合側上經處理之根據本發明之一第二基板14傳輸至具有經準備第一基板1之一結合腔室5中或至經準備第一基板1。在結合腔室5中，在第一基板1之結合側與第二基板14之結合側之間發生結合處理。結合物係熟習此項技術者所知曉的。熟習此項技術者知道如何構造此等系統，如何建造樣本固持器15及/或壓版16，如何發生兩個基板之收斂，如何施加用於結合兩個基板1、14之力，及如何藉由一出口21抽空結合腔室5。可將樣本固持器15組態為一靜電樣本固持器及/或加熱樣本固持器及/或冷卻樣本固持器。較佳地，將樣本固持器15用於傳輸出電漿腔室4。樣本固持器15較佳係一靜電樣本固持器，以確保基板1至樣本固持器15上之良好熱膨脹。機械夾鉗或藉由真空之夾鉗將不容許基板1自由熱膨脹至與靜電樣本固持器15相同之程度。在一非常較佳組態中，樣本固持器15尤其經由內建於樣本固持器15內之一沖洗裝置自前及/或後側使用He清
洗以確保或甚至改良熱耦合。
A
在成功結合處理之後，自動機6拿取藉由自兩個基板1、14之結合產生之結合堆疊且將其較佳儲存在儲存容器8中。
After the successful bonding process, the
1‧‧‧基板 1‧‧‧ substrate
1o‧‧‧基板表面 1o‧‧‧Substrate surface
2、2'、2"‧‧‧氧化物層 2, 2', 2"‧‧‧ oxide layer
2o‧‧‧氧化物層表面 2o‧‧‧Oxide layer surface
3‧‧‧模組群 3‧‧‧Module Group
4‧‧‧電漿腔室 4‧‧‧ plasma chamber
5‧‧‧結合腔室 5‧‧‧Combination chamber
6‧‧‧自動機 6‧‧‧Automata
7‧‧‧工作腔室 7‧‧‧Working chamber
8‧‧‧儲存容器 8‧‧‧Storage container
9‧‧‧下部電極 9‧‧‧Lower electrode
10‧‧‧上部電極 10‧‧‧Upper electrode
11‧‧‧氣體供應器 11‧‧‧ gas supply
12‧‧‧出口 12‧‧‧Export
13‧‧‧電漿氣體 13‧‧‧Plasma gas
14‧‧‧第二基板 14‧‧‧Second substrate
15‧‧‧樣本固持器 15‧‧‧Sample holder
16‧‧‧壓版 16‧‧‧Press version
17‧‧‧凸緣 17‧‧‧Flange
18‧‧‧源 18‧‧‧ source
19‧‧‧偵測器 19‧‧‧ Detector
20‧‧‧結合/電漿腔室 20‧‧‧Combination/plasma chamber
21‧‧‧出口 21‧‧‧Export
22‧‧‧工作空間 22‧‧‧Working space
d、d'‧‧‧氧化物層厚度 d, d'‧‧‧ oxide layer thickness
自較佳組態實例之下文描述及自圖式之參考出現本發明之進一步優點、特徵及細節。其中：圖1a展示具有氧化物層之一基板之一橫截面圖。 Further advantages, features and details of the present invention emerge from the following description of the preferred configuration example and the reference from the drawings. Where: Figure 1a shows a cross-sectional view of a substrate with an oxide layer.
圖1b展示根據本發明之一第一組態之具有藉由電漿改質之氧化物層之來自圖1a之基板， Fig. 1b shows the substrate from Fig. 1a with an oxide layer modified by plasma according to a first configuration of the present invention,
圖1c展示根據本發明之一第二組態之具有藉由電漿減小厚度之氧化物層之來自圖1a之基板，圖1d展示根據本發明之一第三組態之具有藉由電漿完全移除之氧化物層之來自圖1a之基板，圖2展示包括皆附接至工作空間之一結合腔室及與其空間分離之一電漿腔室之根據本發明之一裝置之一第一組態之一示意圖示，圖3展示包括配置在工作空間上之一結合電漿腔室之根據本發明之一裝置之一第二組態之一示意圖示，圖4展示包括多個電漿腔室及一結合腔室之根據本發明之一裝置之一第三組態之一示意表示，圖5展示根據本發明之一電漿腔室之一示意表示，及圖6展示根據本發明之一結合腔室之一示意表示。 FIG. 1c shows the substrate from FIG. 1a with an oxide layer having a reduced thickness by plasma according to a second configuration of the present invention, and FIG. 1d shows a by-plasma with a third configuration according to the present invention. The completely removed oxide layer from the substrate of FIG. 1a, FIG. 2 shows a first of a device according to the present invention including a bonding chamber attached to the working space and a plasma chamber separated from its space A schematic diagram of one configuration is shown in FIG. 3 showing a schematic diagram of a second configuration including a device according to the invention including a plasma chamber arranged on the working space. A schematic representation of a third configuration of a device according to the invention of a plasma chamber and a combination chamber, FIG. 5 shows a schematic representation of a plasma chamber according to the invention, and FIG. 6 shows according to the invention One is combined with a schematic representation of one of the chambers.
3‧‧‧模組群 3‧‧‧Module Group
6‧‧‧自動機 6‧‧‧Automata
7‧‧‧工作腔室 7‧‧‧Working chamber
8‧‧‧儲存容器 8‧‧‧Storage container
20‧‧‧結合/電漿腔室 20‧‧‧Combination/plasma chamber
22‧‧‧工作空間 22‧‧‧Working space
Claims (18)
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| PCT/EP2013/069900 WO2015043624A1 (en) | 2013-09-25 | 2013-09-25 | Apparatus and method for bonding substrates |
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| CN110098138B (en) | 2023-07-18 |
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| KR102182791B1 (en) | 2020-11-26 |
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| WO2015043624A1 (en) | 2015-04-02 |
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